JP2005053853A - Molded product of foamable chlorinated isocyanuric acid - Google Patents

Molded product of foamable chlorinated isocyanuric acid Download PDF

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JP2005053853A
JP2005053853A JP2003287668A JP2003287668A JP2005053853A JP 2005053853 A JP2005053853 A JP 2005053853A JP 2003287668 A JP2003287668 A JP 2003287668A JP 2003287668 A JP2003287668 A JP 2003287668A JP 2005053853 A JP2005053853 A JP 2005053853A
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acid
chlorinated isocyanuric
isocyanuric acid
molded product
sodium sulfate
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Shigeru Morioka
茂 森岡
Yoshiya Iwasaki
好也 岩崎
Yasushi Seo
泰史 瀬尾
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Shikoku Chemicals Corp
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Shikoku Chemicals Corp
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Priority to JP2003287668A priority Critical patent/JP2005053853A/en
Priority to US10/911,496 priority patent/US7651628B2/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/02—Odour removal or prevention of malodour

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded product of a foamable chlorinated isocyanuric acid, having excellent preservation stability, capable of reducing the abrasion of a mortar and a pounder used as a mold at pressure forming thereof, preventing the surfaces of the mortar and the pounder from being damaged, and enabling the use of a lubricant to be reduced. <P>SOLUTION: The molded product of the foamable chlorinated isocyanuric acid is obtained by subjecting a formulated product of 100 pts. wt. chlorinated isocyanuric acid, 50-200 pts. wt. organic acid, 50-200 pts. wt. carbonic acid salt and 10-100 pts. wt. sodium sulfate having ≥45 and <355 μm particle diameter to the pressure forming. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、塩素化イソシアヌル酸、有機酸、炭酸塩及び硫酸ナトリウムを含む配合物を加圧成形したことを特徴とする発泡性塩素化イソシアヌル酸成形物に関するものである。   The present invention relates to a foamable chlorinated isocyanuric acid molded product obtained by pressure molding a compound containing chlorinated isocyanuric acid, an organic acid, carbonate and sodium sulfate.

水溶液中で次亜塩素酸を生成する塩素化イソシアヌル酸は、塩素系酸化剤として知られ、その殺菌、漂白、脱臭等の効果が優れているため、種々の用途に使用されている。この塩素化イソシアヌル酸は、粉末状、顆粒状で使用される他、取り扱い易さの点から錠剤型に加圧成形して使用されることが多い。   Chlorinated isocyanuric acid that generates hypochlorous acid in an aqueous solution is known as a chlorinated oxidant, and is excellent in effects such as sterilization, bleaching, and deodorization, and thus is used in various applications. This chlorinated isocyanuric acid is often used in the form of a powder or granule, and is also used by being pressure-molded into a tablet from the viewpoint of ease of handling.

ところで、塩素化イソシアヌル酸を加圧成形したものは、粉末状のものに比べて、水に接触させた場合の溶解速度が遅くなるので、塩素化イソシアヌル酸と、発泡剤として有機酸および炭酸塩を配合して成形物とすることが広く行われている。例えば特許文献１には、塩素化イソシアヌル酸、アジピン酸と、重炭酸ソーダまたは炭酸ソーダを配合して打錠した発泡性清浄剤が提案されている。   By the way, the pressure-molded chlorinated isocyanuric acid has a lower dissolution rate when brought into contact with water than the powdered one. Therefore, chlorinated isocyanuric acid and organic acids and carbonates as blowing agents are used. It is widely practiced to blend into a molded product. For example, Patent Document 1 proposes an effervescent detergent that is tableted by blending chlorinated isocyanuric acid and adipic acid with sodium bicarbonate or sodium carbonate.

しかしながら、このような発泡性塩素化イソシアヌル酸成形物は、空気中の水分に対して敏感であり、その保管には細心の注意が必要である。即ち、塩素化イソシアヌル酸、有機酸および炭酸塩を含有する成形物を外気に触れる場所に放置しておくと、外気中の湿気を吸収し、塩素化イソシアヌル酸、有機酸および炭酸塩が相互に反応、分解して、塩素系ガスや炭酸ガスを発生する。その結果、前記成形物中の有効塩素含有量が減少すると共に、その発泡力が低下するという問題点があった。
これらの防止の為、発泡性塩素化イソシアヌル酸成形物をアルミニウムを蒸着させたフィルム、或いはアルミニウム箔と積層させたラミネートフィルム等で密閉包装しているが、長期間に渡って高温多湿下で保管した場合には、包装袋が膨張したり破裂する恐れがあり、保存安定性の優れた発泡性成形物が望まれていた。 However, such foamable chlorinated isocyanuric acid molded products are sensitive to moisture in the air, and must be meticulously stored. That is, if a molded product containing chlorinated isocyanuric acid, organic acid and carbonate is left in a place where it is exposed to the outside air, moisture in the outside air is absorbed, and the chlorinated isocyanuric acid, organic acid and carbonate are mutually exchanged. Reacts and decomposes to generate chlorine gas and carbon dioxide gas. As a result, there is a problem that the effective chlorine content in the molded product is reduced and the foaming power is reduced.
To prevent these problems, foamed chlorinated isocyanuric acid molded products are hermetically packaged with aluminum-deposited films or laminated films laminated with aluminum foil, but stored under high temperature and high humidity for a long period of time. In such a case, the packaging bag may expand or rupture, and a foamable molded article having excellent storage stability has been desired.

一方、特許文献２には、６０メッシュ篩（注：目開き２５０μｍ）を通過する大きさの塩素化イソシアヌル酸化合物またはそのアルカリ塩に、３５メッシュ篩（注：目開き４２０μｍ）を通過する硫酸ナトリウムを混合し圧縮成形したのち破砕、篩分して得られた配合安定性の良い塩素化イソシアヌル酸成形物が開示されている。しかしながら、塩素化イソシアヌル酸と有機酸および炭酸塩を含有する塩素化イソシアヌル酸成形物の安定化効果については、何ら記載されていない。   On the other hand, in Patent Document 2, sodium sulfate that passes through a 35-mesh sieve (note: 420 μm openings) is added to a chlorinated isocyanuric acid compound or an alkali salt thereof having a size that passes through a 60-mesh sieve (note: 250 μm openings). A chlorinated isocyanuric acid molded product having good blending stability obtained by crushing and sieving after mixing and compression molding is disclosed. However, there is no description about the stabilizing effect of the chlorinated isocyanuric acid molded product containing chlorinated isocyanuric acid, organic acid and carbonate.

また、一般に硫酸ナトリウムを含有する塩素化イソシアヌル酸成形物を製造するに当たっては、硫酸ナトリウムの結晶の硬度が高く、加圧成形時に金型として使用する臼杵の表面が摩耗したり、傷が付く恐れがあった。このような問題を解決するためには、ステアリン酸マグネシウム、ステアリン酸カルシウムあるいは脂肪酸エステル等の滑沢剤を配合すればよいのであるが、前記の滑沢剤を使用した塩素化イソシアヌル酸成形物を水に溶解させると、その溶解水中に滑沢剤が浮遊物として溶け残り不快な印象を与えるので、風呂水やプール水等には使用し難いものであった。また脂肪酸エステル系の滑沢剤は、塩素化イソシアヌル酸と接触することにより、塩素化イソシアヌル酸が分解して、塩素系のガスが発生するという問題点があった。   In addition, when manufacturing chlorinated isocyanuric acid molded products generally containing sodium sulfate, the hardness of the crystals of sodium sulfate is high, and the surface of the mortar used as a mold during pressure molding may be worn or scratched. was there. In order to solve such a problem, a lubricant such as magnesium stearate, calcium stearate or a fatty acid ester may be blended. A chlorinated isocyanuric acid molded product using the lubricant described above is added to water. If dissolved, the lubricant dissolves in the dissolved water as a suspended matter and gives an unpleasant impression, so that it is difficult to use in bath water or pool water. Further, the fatty acid ester lubricant has a problem in that when it comes into contact with chlorinated isocyanuric acid, the chlorinated isocyanuric acid is decomposed to generate chlorine gas.

特開昭６１−１９２８００号公報JP-A-61-192800 特開平１−１３９５１１号公報JP-A-1-139511

本発明は、優れた保存安定性と共に、加圧成形時に金型として使用する臼杵の摩耗を軽減することができ、且つ臼杵表面に傷を付き難くし、滑沢剤の使用を抑えることができるという特徴を有する発泡性塩素化イソアイアヌル酸成形物を提供することを目的とする。   The present invention can reduce wear of a mortar used as a mold at the time of pressure molding together with excellent storage stability, can hardly damage the surface of the mortar, and can suppress the use of a lubricant. An object of the present invention is to provide a foamable chlorinated isoayanuric acid molded product having the characteristics described above.

本発明者等は、前記の課題を解決するために鋭意研究を重ねた結果、塩素化イソシアヌル酸、有機酸、炭酸塩及び硫酸ナトリウムを含む配合物を加圧成形することにより、優れた保存安定性を有する発泡性塩素化イソシアヌル酸成形物が得られることを見出し本発明を完成するに至ったものである。
また、硫酸ナトリウムの粒径を４５μｍ以上〜３５５μｍ未満とすることにより、加圧成形時に金型として使用する臼杵の摩耗を軽減することができ、且つ臼杵表面に傷を付き難くし、滑沢剤の使用を抑えることができる。そして、前記成形物の保存安定性を更に優れたものとすることができる。 As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have achieved excellent storage stability by pressure molding a compound containing chlorinated isocyanuric acid, organic acid, carbonate and sodium sulfate. It has been found that a foamable chlorinated isocyanuric acid molded product having a property can be obtained, and the present invention has been completed.
Further, by setting the particle diameter of sodium sulfate to 45 μm or more and less than 355 μm, it is possible to reduce the wear of the mortar used as a mold at the time of pressure molding, and it is difficult to damage the surface of the mortar, and a lubricant. The use of can be suppressed. The storage stability of the molded product can be further improved.

本発明の発泡性塩素化イソシアヌル酸成形物は、優れた保存安定性と共に、加圧成形時に金型として使用する臼杵の摩耗を軽減することができ、且つ臼杵表面に傷を付き難くし、滑沢剤の使用を抑えることができるという特徴を有するものであり、プール水、風呂水等の人体が接触する水の殺菌清浄剤として好適に使用することができる。   The foamable chlorinated isocyanuric acid molded product of the present invention has excellent storage stability, can reduce wear of a mortar used as a mold during pressure molding, makes it difficult to scratch the surface of the mortar, It has the feature that the use of a pesticide can be suppressed, and can be suitably used as a sterilizing and cleaning agent for water such as pool water and bath water that come into contact with human bodies.

本発明において使用する塩素化イソシアヌル酸化合物は、トリクロロイソシアヌル酸、ジクロロイソシアヌル酸、ジクロロイソシアヌル酸ナトリウム塩及びその１水和物並びに２水和物、ジクロロイソシアヌル酸カリウム等が挙げられる。
トリクロロイソシアヌル酸およびジクロロイソシアヌル酸は、水に対する溶解度が低く、ジクロロイソシアヌル酸ナトリウム塩及びその１水和物並びに２水和物、ジクロロイソシアヌル酸カリウムは、水に対する溶解度が高いという特性を有している。従って、本発明の発泡性塩素化イソアイアヌル酸成形物を徐々に溶解させる場合には、トリクロロイソシアヌル酸およびジクロロイソシアヌル酸が適しており、該成形物を速やかに溶解させたい場合には、ジクロロイソシアヌル酸ナトリウム塩及びその１水和物並びに２水和物、ジクロロイソシアヌル酸カリウムが好適に使用される。 Examples of the chlorinated isocyanuric acid compound used in the present invention include trichloroisocyanuric acid, dichloroisocyanuric acid, dichloroisocyanuric acid sodium salt and its monohydrate and dihydrate, and potassium dichloroisocyanurate.
Trichloroisocyanuric acid and dichloroisocyanuric acid have low water solubility, and dichloroisocyanuric acid sodium salt and its monohydrate and dihydrate, dichloroisocyanuric acid potassium has the property of high solubility in water. . Therefore, trichloroisocyanuric acid and dichloroisocyanuric acid are suitable for gradually dissolving the foamable chlorinated isoianuric acid molded product of the present invention, and dichloroisocyanuric acid is suitable for rapidly dissolving the molded product. Sodium salt and its monohydrate and dihydrate, potassium dichloroisocyanurate are preferably used.

本発明に使用する有機酸としては、クエン酸、酒石酸、アスコルビン酸、リンゴ酸、フマル酸、コハク酸、マロン酸、アジピン酸、シュウ酸、乳酸等が挙げられる。
本発明に使用する炭酸塩としては、炭酸ナトリウム、重炭酸ナトリウム、炭酸カリウム、重炭酸カリウム、炭酸アンモニウム、セスキ炭酸ナトリウム、過炭酸ナトリウム等が挙げられ、これらのうち炭酸ナトリウム、重炭酸ナトリウムが原料コストが安価である点において好ましい。
これらの有機酸および炭酸塩は、それぞれ１種又は２種以上を組み合わせて用いることができる。
また、有機酸および炭酸塩の配合割合は、塩素化イソシアヌル酸１００重量部に対して、各々５０〜２００重量部であることが好ましいが、有機酸と炭酸塩の配合比率は、酸およびアルカリの当量比において１：１であることが好ましい。 Examples of the organic acid used in the present invention include citric acid, tartaric acid, ascorbic acid, malic acid, fumaric acid, succinic acid, malonic acid, adipic acid, oxalic acid, and lactic acid.
Examples of the carbonate used in the present invention include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, sesquisodium carbonate, sodium percarbonate and the like. Of these, sodium carbonate and sodium bicarbonate are raw materials. This is preferable in that the cost is low.
These organic acids and carbonates can be used alone or in combination of two or more.
Further, the blending ratio of the organic acid and the carbonate is preferably 50 to 200 parts by weight with respect to 100 parts by weight of the chlorinated isocyanuric acid, but the blending ratio of the organic acid and the carbonate is an acid and an alkali. The equivalent ratio is preferably 1: 1.

前記の有機酸および炭酸塩は、発泡剤として作用し、塩素化イソシアヌル酸、有機酸、炭酸塩を含有する成形物を水に投入した場合には、有機酸と炭酸塩が反応し炭酸ガスを発生するので、該成形物が発泡しながら崩壊し、該成形物の溶解速度を速めることができる。   The organic acid and carbonate act as a foaming agent. When a molded product containing chlorinated isocyanuric acid, organic acid and carbonate is added to water, the organic acid and carbonate react to generate carbon dioxide. Therefore, the molded product collapses while foaming, and the dissolution rate of the molded product can be increased.

本発明に使用する硫酸ナトリウムは、結晶水を有するものであっても構わないが、乾燥剤としても作用し得る無水塩を使用することが好ましい。
また、硫酸ナトリウムの粒径は特に限定されないが、４５μｍ以上〜３５５μｍ未満の粒径を有するものが好ましい。硫酸ナトリウムの粒径が４５μｍより小さい場合には、成形時における空気抜きが困難となり所謂キャッピングが発生し易くなる。また、３５５μｍ以上の場合には、成形物を取り出す際に成形物の押し出し圧力が高くなるので、成形時に使用する臼杵の摩耗が促進され、また臼杵表面に傷が付き易くなる。また、本発明の発泡性塩素化イソシアヌル酸成形物の保存安定性の改善効果がやや劣るものとなる。
硫酸ナトリウムの配合割合は、塩素化イソシアヌル酸１００重量部に対して、１０〜１００重量部であることが好ましい。１０重量部より少ない場合には、所期の保存安定性が得られず、１００重量部より多くした場合には、塩素化イソシアヌル酸および発泡剤の配合割合が低下し、有効塩素含有量および発泡性能が低下してしまう。 The sodium sulfate used in the present invention may have crystal water, but it is preferable to use an anhydrous salt that can also act as a desiccant.
Moreover, the particle diameter of sodium sulfate is not particularly limited, but those having a particle diameter of 45 μm or more and less than 355 μm are preferable. When the particle diameter of sodium sulfate is smaller than 45 μm, it is difficult to remove air during molding, and so-called capping is likely to occur. In the case of 355 μm or more, since the extrusion pressure of the molded product is increased when the molded product is taken out, wear of the mortar used at the time of molding is promoted, and the surface of the mortar is easily damaged. Moreover, the improvement effect of the storage stability of the foamable chlorinated isocyanuric acid molded product of the present invention is slightly inferior.
The mixing ratio of sodium sulfate is preferably 10 to 100 parts by weight with respect to 100 parts by weight of chlorinated isocyanuric acid. When the amount is less than 10 parts by weight, the intended storage stability cannot be obtained. When the amount is more than 100 parts by weight, the blending ratio of chlorinated isocyanuric acid and the blowing agent decreases, and the effective chlorine content and foaming are reduced. Performance will be degraded.

更に、本発明の実施においては、風呂水、プール水以外の用途に使用する場合には、必要に応じてステアリン酸マグネシウム、ステアリン酸カルシウム、タルク等の滑沢剤を配合しても差し支えない。   Furthermore, in the practice of the present invention, when used for purposes other than bath water and pool water, lubricants such as magnesium stearate, calcium stearate, and talc may be blended as necessary.

本発明の発泡性塩素化イソシアヌル酸成形物は、常法に従って塩素化イソシアヌル酸、有機酸、炭酸塩および硫酸ナトリウムを混合し、加圧して成形物とすることができる。
本発明の発泡性塩素化イソシアヌル酸成形物の形状は、顆粒状、ブリケット状、錠剤等の何れの形状であっても構わない。 The foamable chlorinated isocyanuric acid molded product of the present invention can be formed into a molded product by mixing and pressurizing chlorinated isocyanuric acid, organic acid, carbonate and sodium sulfate according to a conventional method.
The shape of the foamable chlorinated isocyanuric acid molded product of the present invention may be any shape such as granules, briquettes, tablets and the like.

本発明の発泡性塩素化イソシアヌル酸成形物は、風呂水、プール水等の殺菌消毒に限定されるものではなく、成形物の形状や大きさを適宜選択することにより、クーリングタワー等の冷却水、防火用水、湖沼等での微生物や藻の繁殖、悪臭発生等を防止する目的にも広く適用できる。   The foamable chlorinated isocyanuric acid molded product of the present invention is not limited to sterilization and disinfection such as bath water and pool water, but by appropriately selecting the shape and size of the molded product, cooling water such as a cooling tower, It can also be widely applied for the purpose of preventing the proliferation of microorganisms and algae in the water for fire prevention, lakes, etc., and the generation of malodor.

以下、実施例および比較例によって本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、実施例および比較例において使用した原料ならびに評価試験方法は、次のとおりである。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to these Examples.
The raw materials and the evaluation test methods used in Examples and Comparative Examples are as follows.

［原料］
・無水ジクロロイソシアヌル酸ナトリウム（四国化成工業社製、有効塩素量：６３．５％）
・アジピン酸（和光純薬工業社製、試薬）
・フマル酸（和光純薬工業社製、試薬）
・重炭酸ナトリウム（和光純薬工業社製、試薬）
・炭酸ナトリウム（和光純薬工業社製、試薬）
・無水硫酸ナトリウム（四国化成工業社製、篩分により、(A)45μm以上〜150μm未満、(B)150μm以上〜355μm未満、(C)355μm以上〜500μm未満の粒径を有するものを調製した） [material]
・ Anhydrous sodium dichloroisocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd., effective chlorine content: 63.5%)
Adipic acid (Wako Pure Chemical Industries, reagent)
・ Fumaric acid (Wako Pure Chemical Industries, Reagent)
・ Sodium bicarbonate (Wako Pure Chemical Industries, Reagent)
・ Sodium carbonate (Wako Pure Chemical Industries, reagent)
・ Anhydrous sodium sulfate (made by Shikoku Kasei Kogyo Co., Ltd., sieved to prepare particles having a particle size of (A) 45 μm to less than 150 μm, (B) 150 μm to less than 355 μm, (C) 355 μm to less than 500 μm )

［保存安定性試験(1)］
５．５ｇの錠剤５個を１Ｌのポリ容器に入れ、内蓋に分解ガス測定用の開穴を設け粘着テープで密閉し、４０℃、相対湿度７５％に設定した恒温恒湿器内に保管して、３０日間および６０日間経過後に、ポリ容器内に発生した塩素ガスとクロラミンガス濃度を検知管（ガステック社製、型番No.8）を使用して測定した。これらの分解ガス濃度が低いほど、保存安定性が優れているものと判定した。 [Storage stability test (1)]
Put 5 5.5g tablets in a 1L plastic container, open a cracked gas measurement hole in the inner lid, seal with adhesive tape, and store in a constant temperature and humidity chamber set at 40 ° C and relative humidity 75%. Then, after 30 days and 60 days had elapsed, the chlorine gas and chloramine gas concentrations generated in the plastic container were measured using a detector tube (manufactured by Gastec, model No. 8). The lower the decomposition gas concentration, the better the storage stability.

［発泡試験］
１Ｌの温水（４０℃）を入れた２Ｌのビーカーに錠剤を投入し、錠剤の発泡開始から発泡終了までの時間を計測し発泡時間とした。一般的には、錠剤中に含まれる有機酸および炭酸塩の含有量が多いものほど、錠剤が水に接触した場合に錠剤が発泡し、錠剤の膨潤崩壊が速やかに進行するので、発泡時間が短くなる。 [Foaming test]
The tablets were put into a 2 L beaker containing 1 L of warm water (40 ° C.), and the time from the start of foaming to the end of foaming was measured and used as the foaming time. In general, the higher the content of organic acid and carbonate contained in the tablet, the more the tablet foams when the tablet comes into contact with water, and the swelling and disintegration of the tablet proceeds more rapidly. Shorter.

［保存安定性試験(2)］
５．５ｇの錠剤５個をポリプロピレン製フィルム（厚さ７０μ）の包装袋に入れ、ヒートシールを行って密封した。この包装物を、４０℃、相対湿度７５％に設定した恒温恒湿器に入れて、６０日間加温加湿を行った。加温加湿の前後で、錠剤の重量を測定し、加温加湿後の錠剤の吸湿量（％）を算出した。また、加温加湿の前後で錠剤の発泡試験を行って、錠剤の発泡時間を測定した。吸湿量が少ないほど、また発泡時間が短いほど、保存安定性が優れているものと判定した。 [Storage stability test (2)]
Five 5.5 g tablets were put into a packaging bag of polypropylene film (thickness 70 μ) and sealed by heat sealing. This package was placed in a thermo-hygrostat set to 40 ° C. and relative humidity 75%, and heated and humidified for 60 days. The weight of the tablet was measured before and after warming and humidification, and the moisture absorption amount (%) of the tablet after warming and humidification was calculated. Moreover, the foaming test of the tablet was performed before and after heating and humidification, and the foaming time of the tablet was measured. It was determined that the smaller the moisture absorption amount and the shorter the foaming time, the better the storage stability.

［実施例１］
無水ジクロロイソシアヌル酸ナトリウム１００重量部、有機酸としてアジピン酸５３重量部及びフマル酸４４重量部、炭酸塩として重炭酸ナトリウム３０重量部及び炭酸ナトリウム４０重量部と、４５μｍ以上〜１５０μｍ未満の粒径を有する無水硫酸ナトリウム６７重量部を混合して配合物を調製した。
前記配合物５．５ｇを、直径２０ｍｍの臼杵に入れ、１０００ｋｇ／ｃｍ２で加圧して錠剤を作成した。得られた錠剤について評価試験を行ったところ、試験結果は表１に示したとおりであった。また、前記配合物２０ｇを、直径３０ｍｍの臼杵に入れ、１０００ｋｇ／ｃｍ２で加圧した後、臼杵内にある成形物を取り出す為に必要な押し出し圧力を測定した。この押し出し圧力は、表１に示したとおりであった。 [Example 1]
100 parts by weight of anhydrous sodium dichloroisocyanurate, 53 parts by weight of adipic acid and 44 parts by weight of fumaric acid as organic acids, 30 parts by weight of sodium bicarbonate and 40 parts by weight of sodium carbonate, and a particle size of 45 μm or more but less than 150 μm A blend was prepared by mixing 67 parts by weight of anhydrous sodium sulfate.
5.5 g of the blend was put into a mortar with a diameter of 20 mm and pressed at 1000 kg / cm 2 to prepare a tablet. When an evaluation test was performed on the obtained tablets, the test results were as shown in Table 1. Further, 20 g of the blend was put into a 30 mm diameter mortar and pressurized at 1000 kg / cm 2 , and then the extrusion pressure necessary to take out the molded product in the mortar was measured. This extrusion pressure was as shown in Table 1.

［実施例２］
１５０μｍ以上〜３５５μｍ未満の粒径を有する無水硫酸ナトリウムを使用した以外は、実施例１と同様にして配合物を調製し、直径２０ｍｍの錠剤を作成し評価試験を行った。また、前記配合物を実施例１と同様にして、直径３０ｍｍの臼杵に入れて加圧し、臼杵内にある成形物を取り出す為に必要な押し出し圧力を測定した。
これらの試験結果は、表１に示したとおりであった。 [Example 2]
A formulation was prepared in the same manner as in Example 1 except that anhydrous sodium sulfate having a particle size of 150 μm or more to less than 355 μm was used, and a tablet having a diameter of 20 mm was prepared and evaluated. Further, in the same manner as in Example 1, the blend was put in a 30 mm diameter mortar and pressed, and the extrusion pressure necessary to take out the molded product in the mortar was measured.
The test results were as shown in Table 1.

［実施例３］
３５５μｍ以上〜５００μｍ未満の粒径を有する無水硫酸ナトリウムを使用した以外は、実施例１と同様にして配合物を調製し、直径２０ｍｍの錠剤を作成し評価試験を行った。また、前記配合物を実施例１と同様にして、直径３０ｍｍの臼杵に入れて加圧し、臼杵内にある成形物を取り出す為に必要な押し出し圧力を測定した。
これらの試験結果は、表１に示したとおりであった。 [Example 3]
A formulation was prepared in the same manner as in Example 1 except that anhydrous sodium sulfate having a particle size of 355 μm or more and less than 500 μm was used, and a tablet having a diameter of 20 mm was prepared and evaluated. Further, in the same manner as in Example 1, the blend was put in a 30 mm diameter mortar and pressed, and the extrusion pressure necessary to take out the molded product in the mortar was measured.
The test results were as shown in Table 1.

［比較例１］
無水ジクロロイソシアヌル酸ナトリウム１００重量部、固体酸としてアジピン酸７４重量部及びフマル酸６１重量部、炭酸塩として重炭酸ナトリウム４３重量部及び炭酸ナトリウム５６重量部を混合して調製した配合物５．５ｇを、直径２０ｍｍの臼杵に入れ、１０００ｋｇ／ｃｍ２で加圧して錠剤を作成した。
得られた錠剤について評価試験を実施したところ、得られた試験結果は、表１に示したとおりであった。 [Comparative Example 1]
5.5 g of a mixture prepared by mixing 100 parts by weight of anhydrous sodium dichloroisocyanurate, 74 parts by weight of adipic acid and 61 parts by weight of fumaric acid as solid acids, 43 parts by weight of sodium bicarbonate and 56 parts by weight of sodium carbonate as carbonates Was put into a mortar with a diameter of 20 mm and pressed at 1000 kg / cm 2 to prepare a tablet.
When the evaluation test was implemented about the obtained tablet, the obtained test result was as showing in Table 1.

Figure 2005053853
Figure 2005053853

表１の試験結果によれば、実施例の無水硫酸ナトリウムを含有する塩素化イソシアヌル酸錠剤は、比較例の無水硫酸ナトリウムを含有しない塩素化イソシアヌル酸錠剤に比べて、加温加湿後の塩素ガスおよびクロラミンガスの発生が抑えられており、優れた保存安定性を有するものと認められる。また、無水硫酸ナトリウムの粒径を、４５μｍ以上〜３５５μｍ未満とすることにより、保存安定性を更に高めることができる。即ち、塩素化イソシアヌル酸の分解を抑制する為には、３５５μｍ未満の粒径を有する無水硫酸ナトリウムを使用することが有効である。   According to the test results of Table 1, the chlorinated isocyanuric acid tablets containing anhydrous sodium sulfate of the Examples were compared with the chlorinated isocyanuric acid tablets of Comparative Example not containing anhydrous sodium sulfate, and the chlorine gas after heating and humidification Further, the generation of chloramine gas is suppressed, and it is recognized as having excellent storage stability. Moreover, storage stability can be further improved by making the particle size of anhydrous sodium sulfate into 45 micrometers or more and less than 355 micrometers. That is, in order to suppress decomposition of chlorinated isocyanuric acid, it is effective to use anhydrous sodium sulfate having a particle size of less than 355 μm.

また、実施例１、２の４５μｍ以上〜１５０μｍ未満の粒径と１５０μｍ以上〜３５５μｍ未満の粒径を有する無水硫酸ナトリウムを含有した塩素化イソシアヌル酸錠剤は、加温加湿前後の発泡時間に差が認められないが、実施例３の３５５μｍ以上〜５００μｍ未満の粒径を有する無水硫酸ナトリウムを含有させた錠剤および比較例１の無水硫酸ナトリウムを含有しない塩素化イソシアヌル酸錠剤は、加温加湿後に発泡時間が長くなっている。この理由は、４５μｍ以上〜３５５μｍ未満の粒径を有する無水硫酸ナトリウムを使用することにより、炭酸塩の分解が抑えられた為と思われる。   Moreover, the chlorinated isocyanuric acid tablets containing anhydrous sodium sulfate having a particle size of 45 μm or more to less than 150 μm and a particle size of 150 μm or more to less than 355 μm in Examples 1 and 2 have a difference in foaming time before and after heating and humidification. Although not recognized, the tablet containing anhydrous sodium sulfate having a particle size of 355 μm to less than 500 μm in Example 3 and the chlorinated isocyanuric acid tablet not containing anhydrous sodium sulfate in Comparative Example 1 were foamed after warming and humidification. The time is getting longer. The reason seems to be that decomposition of carbonate was suppressed by using anhydrous sodium sulfate having a particle size of 45 μm or more and less than 355 μm.

更には、実施例１、２の４５μｍ以上〜１５０μｍ未満の粒径と１５０μｍ以上〜３５５μｍ未満の粒径を有する無水硫酸ナトリウムを含有する塩素化イソシアヌル酸錠剤は、臼杵から取り出す際に約１５０ｋｇ／ｃｍ２の押し出し圧で取り出すことができるが、実施例３の３５５μｍ以上〜５００μｍ未満の粒径を有する無水硫酸ナトリウムの場合には、成形物を臼杵から取り出す際に約２５０ｋｇ／ｃｍ２の押し出し圧を必要とした。即ち、実施例１、２の３５５μｍ未満の粒径を有する無水硫酸ナトリウムを含有する塩素化イソシアヌル酸成形物は、臼杵との摩擦抵抗が少ないからであり、３５５μｍ以上〜５００μｍ未満の粒径を有する無水硫酸ナトリウムの場合に比べて、臼杵の摩耗を低減させることができる。 Furthermore, the chlorinated isocyanuric acid tablets containing anhydrous sodium sulfate having a particle size of 45 μm to less than 150 μm and a particle size of 150 μm to less than 355 μm of Examples 1 and 2 are about 150 kg / cm when taken out from the mortar. In the case of anhydrous sodium sulfate having a particle size of 355 μm or more and less than 500 μm in Example 3, an extrusion pressure of about 250 kg / cm 2 is applied when the molded product is taken out from the mortar. I needed it. That is, the chlorinated isocyanuric acid molded product containing anhydrous sodium sulfate having a particle size of less than 355 μm in Examples 1 and 2 has a low frictional resistance with a mortar and has a particle size of 355 μm or more to less than 500 μm. As compared with the case of anhydrous sodium sulfate, the wear of the mortar can be reduced.

Claims (3)

塩素化イソシアヌル酸、有機酸、炭酸塩及び硫酸ナトリウムを含む配合物を加圧成形したことを特徴とする発泡性塩素化イソシアヌル酸成形物。 A foamable chlorinated isocyanuric acid molded product obtained by pressure-molding a compound containing chlorinated isocyanuric acid, organic acid, carbonate and sodium sulfate. 塩素化イソシアヌル酸１００重量部、有機酸５０〜２００重量部、炭酸塩５０〜２００重量部及び硫酸ナトリウム１０〜１００重量部を含む配合物を加圧成形したことを特徴とする発泡性塩素化イソシアヌル酸成形物。 Foaming chlorinated isocyanuric, characterized in that it is pressure-molded with a composition containing 100 parts by weight of chlorinated isocyanuric acid, 50 to 200 parts by weight of organic acid, 50 to 200 parts by weight of carbonate and 10 to 100 parts by weight of sodium sulfate. Acid molded product. 硫酸ナトリウムの粒径が、４５μｍ以上〜３５５μｍ未満であることを特徴とする請求項１または請求項２記載の発泡性塩素化イソシアヌル酸成形物。 The foamable chlorinated isocyanuric acid molded article according to claim 1 or 2, wherein the particle diameter of sodium sulfate is 45 µm or more and less than 355 µm.
JP2003287668A 2003-08-06 2003-08-06 Molded product of foamable chlorinated isocyanuric acid Pending JP2005053853A (en)

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